Anthraquinone dye compounds



United States Patent ANTHRAQUIN ONE DYE COMPOUNDS James M. Straley andRalph R. Giles, Kingsport, Tenn., assignors to Eastman Kodak Company,Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Mar. 10,1958, Ser. No. 720,024 7 Claims. (Cl. 260377) This invention relates tonew anthraquinone compounds and their application to the art of dyeingor coloring.

The dyeing of polyester textile materials, such as polyethyleneterephthalate, has presented difliculties. While it is known that thefamiliar disperse dyes, that is waterinsoluble dyes, employed for thecoloration of cellulose acetate frequently possess aflinity forpolyester textile materials such as polyethylene terephthalate,'-by farthe majority of the known disperse dyes for cellulose acetate exhibitpoor fastness to light when applied to polyester textile materials. Thenew water-insoluble anthraquinone compounds of our invention possessgood aflinity for polyester textile materials and give red dyeingsthereon having good fastness properties, including good fastness -tolight. Additionally, they have good aflinity for cellulose acetate, forexample, and yield dyeings of high quality thereon.

Polyester fabrics are usually heat set, after dyeing, at temperatureswhich often reach 400 F. If the dye is not fast to sublimation it willbe removed in part, at least, from the goods during this operation. Somedyes, otherwise suitable for dyeing polyester fabrics, are unsuitablebecause they are not fast to sublimation. The new anthraquinonecompounds of our invention yield dyeings on the textile materialsindicated herein which have excellent fastness to sublimation.

Similarly, dyeings desirably should be fast to solvent rubbing. When adry cleaner receives a garment he may wish to remove the heavier stainsby rubbing the garment with a solvent prior to putting it with othergarments. If the dyeing is not resistant to this treatment the spot orspots rubbed with solvent will become lighter in shade. Theanthraquinone compounds of our invention yield dyeings on the textilematerials indicated herein which have satisfactory resistance to solventrubbing.

It is an object of our invention to provide new anthraquinone compounds.Another object is to provide a satisfactory process for the preparationof our new anthraqul'none compounds. A further object is to provide dyedpolyester textile materials which have good fastness prop erties.Another object is to provide dyed cellulose alkyl carboxylic acid estertextile materials which have good fastness properties. A particularobject is to provide dyed polyethylene terephthalate textile materialswhich have good fastness properties. A further particular object is toprovide dyed cellulose acetate textile materials which have goodfastness properties.

We havediscovered that the anthraquinone compounds having the formula:

wherein X represents a methyl group, an ethyl group, a fl-methoxyethylgroup or a ,B-ethoxyethyl group and Y represents an alkyl hydrocarbongroup having 4 to 8 carbon atoms or a cyclohexyl group are valuable dyesfor coloring polyester and cellulose alkyl carboxylic acid ester having2 to 4 carbon atoms in the acid groups thereof textile materials. Thesedye compounds when applied to the aforesaid textile materials have goodafiinity therefor and give red dyeings of high quality. In general thedyeings obtained have excellent fastness, for example, to light, gas,washing and sublimation.

By cellulose alkyl carboxylic acid esters having two to four carbonatoms in the acid groups thereof, we mean to include, for example, bothhydrolyzed and unhydrolyzed cellulose acetate, cellulose propionate,cellulose butyrate, cellulose acetate-propionate and celluloseacetate-butyrate.

The polyester textile materials that can be dyed with the newanthraquinone compounds of our invention include polyethyleneterephthalate textile materials obtained for example as described in US.Patent 2,465,319, patented March 22, 1949, or other polyester textilematerials formed from analogous fiber-forming linear polyesters, such aspolyesters derived from p,p-sulfonyldibenzoic acid and various aliphaticacids and glycols as described in US. Patent 2,744,088, patented May 1,1956, and polyesters derived from various acids, such as terephthalicacid, and 1,4-cyclohexanedimethanol as described in Kibler, Bell andSmith US. application Serial No. 554,639, filed December 22, 1955, nowU.S. Patent No. 2,901,466. Dacron (polyethylene terephthalate) andcellulose acetate are specific illustrations of the textile materialsthat can be dyed with our new anthraquinone compounds.

The new anthraquinone compounds of our invention can be prepared bycondensing a 1,4-diaminoanthraquinone compound having the formula:

ii 0 NH:

wherein X represents a methyl group, an ethyl group, a fi-methoxyethylgroup or a p-ethoxyethyl group with a haloformic acid ester having theformula:

wherein Y represents an alkyl hydrocarbon group having 4 to 8 carbonatoms or -a cyclohexyl group and Z represents a chlorine atom or abromine atom. We prefer to use chloroformic acid esters because theseesters are readily prepared from simple starting materials; namely,phosgene and the requisite alcohol.

We prefer to carry out the condensation reaction be tween the1,4-diaminoanthraquinone and the haloformic acid ester compound in aneutral, organic solvent for the reactants employed which is inert underthe reaction conditions employed. While solvents other than thosespecifically disclosed herein can be used we prefer to use, for example,ethers of ethylene glycol such as ethylene glycol monomethyl ether andethylene glycol monoas the monomethyl ether of diethylene glycol and themonoethyl ether or diethylene glycol, for example, nitrobenzene,dichlorobenzene and trichlorobenzene because suitable reactiontemperatures can be obtained and the solubility characteristics of thestarting materials and the reaction products are well suited to thesesolvents,

Other suitable solvents are hydrocarbons such as Solvesso 100,predominately aromatic, boiling at about 160-190 C. As a practicalmatter we prefer to use temperatures in excess of 100 C. Temperatures ofabout 110 C. to about 145 C. appear to be very prac-, tical.Temperatures lower than 100 C. can be used but are not practical becauseof the increased reaction time required. Similarly, temperatures higherthan 145 C. can be employed if desired.

The use of the solvents indicated hereinbefore permits the reaction tobe carried out readily at a suitable temperature. The boiling points ofthe solvents namedare such that by maintaining the reaction mixtureunder reflux a satisfactory reaction temperature results.

1,4 diamino-2-methoxyanthraquinone, 1,4-diamino-2- ethoxyanthraquinone,1,4-diamino-2-;3-methoxyethoxyanthraquinone and1,4-diamino-2-fi-ethoxyethoxyanthraquinone are used in the preparationof the new anthraquinone compounds of our invention when prepared inaccordance with the process described herein. Isobutyl chloroformate,n-butyl chloroformate, sec-butyl chloroformate, n-amyl chloroformate,isoamyl chloroformate, isoamyl brornoformate, n-hexyl chloroformate,n-heptyl chloroformate, Z-ethylhexyl chloroformate, 1-methylheptylchloroformate and n-octyl chloroformate are illustrative of thehaloformic acid ester compounds used in the preparation of theanthraquinone compounds of our invention.

The following examples illustrate the anthraquinone compounds and theprocess of our invention.

EXAMPLE 1 10 grams, of 1,4;diamino-Z-methoxyanthraquinone, 10

gramsof n-arnyl chloroformate and lcc. of ethylene glycolmonomethylether were refluxed together with stirringuntilevolution of hydrogenchloride was complete.

g+ -o-onrontontontcnr and dyes polyethylene terephthalate and celluloseacetate textile materials, for example, bright red shades havingexcellent fastness to light, gas, washing and sublimation.

EXAMPLE 2 1 gram of 1,4-diamino-2-methoxyanthraquinone, 1 gram 7 ofisobutyl chloroformate and cc. of nitrobenzene were heated together atabout 120 C.-125 C., with stirring,-

until no further color change was observed. The reaction mixture wasthen cooled to 80 C., diluted with 2 volumes of methanol, and cooled to0 C. and kept at this temperature for 3 hours. The reaction productwhichprecipated was recovered by filtration, washed well with methanoland dried. 1.1 grams of I-ami-no-Z-methoxy-4-isobutoxy-carbamylanthraquinone was obtained. It

dyes Dacron and cellulose acetate textile materials for example,'bnghtred shades havingexcellent fastness to light and sublimation,forexample. EXAMPLE 3 Bythe use of 10 grams of n-hexyl clloroformate'in'place of n-amyl' chloroformate in EXample 1, l-amino-2-methoxy-4-n-hexoxycarbamylanthraquinone is obtained; It dyes Dacronand cellulose acetate textile materials; for

example, red shades having excellent fastness to light and sublimation,for example.

EXAMPLE 4 By the use of 1 gram of cyclohexyl chloroformate in place ofisobutyl chloroformate in Example 2, 1-amino-2-rnethoxy-4-cyclohexoxycarbamylanthraquinone was obtained. It dyes Dacronand cellulose acetate textile materials, for example, bright fast redshades.

EXAMPLE 5 By the use of 10 grams of 2-ethylhexyl chloroformate in placeof n-amyl chloroformate in Example 1, 12.4 grams of1-amino-2-methoxy-4-(Z-ethylhexoxy)carbamylanthraquinone were obtained.It dyes Dacron and cellulose acetate textile materials, for example,beautiful red shades having excellent fastness, for example, to light,sublimation and washing.

EXAMPLE 6 for example, to light, sublimation and washing.

EXAMPLE 7 By the use of 2.5 grams of n-octyl chloroformate in place ofn-heptyl chloroformate in Example 6, 1.6-gram of1-amino-2-methoxy-4-n-octoxycarbamylanthraquinone was obtained; It dyesDacron'textile materials bright red shades which are fast, for example,to light, sublima tion and washing.

EXAMPLE 8 By the use of 11 grams of 1,4-diamino-2-ethoxyanthraquinone inplace of 1,4-diamino-2-methoxyanthraquinone in Example 1,1-amino-2-ethoxy-4-n-amoxycarbamylanthraquinone is obtained. It dyesDacron textile materials bright red shades having excellent fastness,for example, to light, gas, washing and sublimation.

BXAMPLE9 1 i of 1,4 diamino 2-j3-methoxyethoxyanthraqub,

none, 2 grams of n-amyl chloroformate and 5 cc. of methyl Cellosolve arerefluxed together until no further color change takes place. Thereaction mixture is then cooled to about C., diluted with twice itsvolume of water and then chilled to 0 C. The reaction product(l-amino-2-,B-methoxyethoxy 4 n-amoxycarbamylanthraquinone) whichprecipitated was recovered by filtration, washed with methyl alcohol andthen dried. About 1.2 gram of dye is obtained.

EXAMPLE l0 cyclohexoxycarbamylanthraquinone) which precipitates is:

recovered by filtration, washed with methyl alcohol and dried. It dyesDacron textile materials bright red shades which are fast to light,washing and sublimation, for example.

Following the procedures described hereinbefore1-amino-2-methoxy-4-n-butoxycarbamylanthraquinone,1-amino-2-methoxy-4-isoamoxycarbamylanthraquinonc,1-amino-2-ethoxy-4-n-butoxycarbamylanthraquinone,

It dyes Dacron I textile materials beautiful red shades which-are fast,-

none,

1-amino-Z-ethoxy-4-cyclohexoxycarbamylanthraquinone,

1 g amino-2-;8-methoxyethoxy-4-isobutoxycarbamylanthraquinone, I

1 amino-2-,B-methoxyethoxy-4-n-hexoxycarbamylanthraquinone,

1 amino-2-fl-methoxyethoxy-4-(2-ethylhexoxy)carbamylanthraquinone, 1 1

1-amino-2-p-methoxyethoxy 4 cyclohexoxycarbamylanthraquinone, I H Il-amino-Z-fl-ethoxyethoxy 4 n butoxycarbamylanthraquinone,

l-amino 2 p ethoxyethoxy-4-n-amoxycarbamylanthraquinone, and

l-amino 2 p ethoxyethoxy-4-(2-ethylhexoxy)carbamylanthraquinone,

for example, are readily prepared. All these compounds yield red dyeingson the textile materials disclosed herein which have fastness propertiesof the character set forth hereinbefore.

Many of the intermediates used in the preparation of the newanthraquinone dye compounds of the invention are old. However, certainof the intermediates appear to be new and, accordingly, examplesillustrating the preparation of the intermediate compounds are givenhereinafter, even though the manner in which they are prepared isbelieved to be clear from the prior art.

EXAMPLE 11 Preparation of 1,4-diamino-Z-fl-methoxyethoxyanthraquinone 5grams of 1-amino-4-p-toluenesulfonamidoanthraquinone-Z-sulfonic acidwere added portionwise, with stirring, at 80 C. over a period of about 1hour to a melt prepared from grams of KOH in 30 cc. of methyl Cellosolveand the reaction mixture resulting was stirred 2 hours longer at 80-85C. The reaction mixture was then colled to 40 C. and run into 500 cc. ofcold water. The product which precipitated was recovered by filtration,washed with hot water and then dried.

The product obtained as described above was dissolved 'by stirring in 50grams of 96% H 80 and after complete solution held at 45-50 C. for 1%hours. The solution thus obtained was then drowned in 1000 cc. of waterwhile keeping the temperature below C. 1,4-diamino-Z-B-methoxyethoxyanthraquinone precipitated and was recovered byfiltration, washed with cold water until neutral to Congo red and thendried.

EXAMPLE 12 Preparation of 1,4-diamino-Z-fl-ethoxyethoxyanthraquinoneEXAMPLE 13 Preparation of Z-ethylhexyl chloroformate Into a 3-neck flaskfitted with a stirrer, gas-inlet tube and Dry Ice trap, cooled in anice-HCl bath, phosgene was run from a tank until 150 cc. of phosgene hadcollected in the flask. The stirrer was started and 130 grams ofZ-ethylhexanol were added dropwise. After complete addition of the2-ethylhexanol, the Dry Ice trap was removed and the excess phosgene wasdistilled ofi by allowing the temperature to rise to room temperature.The residue in the flask was washed with ice water, dried over CaCl anddistilled under a vacuum of about 2 mm. The fraction boiling at 65-66C./2 mm. was collected and consisted essentially of Z-ethylhexylchloroformate. The yield was 149.7 grams.

6 EXAMPLE 14 Preparation of n-heptyl chlorof'ormate Example 13 wasrepeated except that grams of n-heptyl alcohol were used in place of2-ethylhexanol and the vacuum distillation was carried out at a pressureof about 4 mm. 83.5 grams of n-heptyl chloroformate boiling at 6062 C./4mm. were obtained.

n-octyl alcohol were used in place of Z-ethylhexanol and.

the vacuum distillation was carried out at a pressureof about 8 mm. 94grams of n-octyl chloroformate boiling at 78-80 C./ 8 mm. wereobtained.1 V

The new anthraquinone compounds of our invention can be used to colorthe polyester and the cellulose alkyl carboxylic acid ester textilematerials mentioned hereinbefore by methods well known to those skilledin the art to which this invention is directed. They may be directlyapplied to the material undergoing coloration in the form of an aqueoussuspension which can be prepared by grinding them to a paste in thepresence of a sulfonated oil, soap, sodium lignin sulfonate, or othersuitable dispersing agent and dispersing the resulting paste in water.

In the case of cellulose alkyl carboxylic acid ester textile materialsdirect dyeing operations can, with advantage, be conducted attemperatures of about 7090 C., but any suitable temperature can be used.Thus, the textile material such as cellulose acetate, for example, to bedyed or colored is ordinarily added to the dye bath at a temperaturelower than that at which the main portion of the dyeing is to beeffected, a temperature approximating 45 C.55 C., for example, followingwhich the temperature is raised to that selected for carrying out thedyeing operation.

While the temperatures given in the dyeing procedure just set forthapply primarily to cellulose alkyl carboxylic acid ester textilematerials, with the modifications indicated hereinafter, this dyeingprocedure also applies to the dyeing of polyester textile materials. Asunderstood by those skilled in the dyeing art somewhat highertemperatures than those set forth in the preceding paragraph areordinarily employed when polyester textile materials, such as Dacron,are being dyed. These latter materials are ordinarily dyed at the boiland usually an assistant, commonly known as a carrier is employed. Thecarriers have various active ingredients, such as chlorinated benzenesand o-phenylphenol, for example, in emulsion. Dacronyx is the tradenameof an illustrative suitable carrier.

As is understood by those skilled in the dyeing art, the intensity ofdyeing can be varied by varying the proportion of dye to materialundergoing coloration. The amount of dye used can be, for example, /s%to 3% (by weight) of that of the textile material, although lesser orgreater amounts of dye can be used.

We claim: 1. The anthraquinone compounds having the formula:

(I? NHr OX wherein X represents a member selected from the groupconsisting of a methyl group, an ethyl group, a p-methoxyethyl group anda p-ethoxyethyl group and Y represents a member selected from the groupconsisting of an alkyl

1. THE ANTHRAQUINONE COMPOUNDS HAVING THE FORMULA: